CN108329484A - Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof - Google Patents
Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof Download PDFInfo
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- CN108329484A CN108329484A CN201810172886.6A CN201810172886A CN108329484A CN 108329484 A CN108329484 A CN 108329484A CN 201810172886 A CN201810172886 A CN 201810172886A CN 108329484 A CN108329484 A CN 108329484A
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Abstract
The invention discloses double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof, and this method comprises the following steps：(1) sodium acetate solution is instilled in iron nitrate solution and is stirred, obtain iron cluster.(2) terephthalic acid (TPA) and triethylene diamine are dissolved in N, in N dimethylformamides, then instill the DMF solution of iron cluster, glacial acetic acid is then added dropwise, stirs evenly；Mixed liquor is packed into vial interior sealing, then carries out temperature programmed control solvent-thermal process reaction, obtains the double ligand metal organic framework materials of iron-based.The material has the characteristic of Preferential adsorption ethane, and the adsorptive selectivity of the adsorption capacity and ethane/ethylene to ethane is all in international most advanced level, under equal conditions, the material is to 2.5 times or more that the adsorption capacity of ethane is activated carbon, selectivity to ethane/ethylene is the 2 times or more of activated carbon, and steam has good stability.Separation of the material for industrial ethylene-ethane, has a good application prospect.
Description
Technical field
The present invention relates to ethylene-ethane adsorption separation technology fields, and in particular to a kind of iron-based of Preferential adsorption ethane is double to match
Body metal-organic framework materials and the preparation method and application thereof.
Background technology
Ethylene is a kind of important petrochemical materials, is widely used in and prepares polystyrene, polyethylene, polyester and other
Chemicals.Industrial ethylene is greatly mostly from the thermal cracking of the cracking of oil and ethane, while thermal cracking prepares ethylene,
Inevitably have the generation of by-product ethane.Since ethylene-ethane has similar boiling point and molecular dimension, from ethane
It is extremely challenging with ethylene is detached in mixture of ethylene.The isolation technics of ethylene-ethane generally uses cryogenic separation in traditional industry
Method, this method are needed in low temperature（-25℃）And high pressure（About 23bar）Under operated, which extremely consumes energy.In order to reduce point
Energy consumption from ethylene-ethane, seeks a kind of low power consuming and efficient isolation technics is significant.Adsorption separation technology has because of it
It consumes energy low, easy to operate, the advantages that equipment investment is small, for the separation great potential of ethylene-ethane mixture.
Adsorbent is the core of adsorption separation technology.The conventional adsorbents such as active carbon molecular sieve are used for adsorbing separation ethylene second
Alkane, exist it is relatively low to ethylene absorption capacity, and to the selectively poor problem of ethylene/ethane separation.In order to solve traditional absorption
The problem that adsorption capacity existing for agent is low and selectivity is relatively low, researchers always strive to develop some novel adsorbents.
Metal-organic framework materials（MOFs）As a kind of novel adsorbent, because it is with high-specific surface area, Gao Kongrong, pore structure
The series of advantages such as controllable, therefore there is larger application prospect for the separation of ethylene-ethane mixture.It is existing at present to be permitted
The MOFs adsorbents of more Preferential adsorption ethylene have been reported for separation ethylene-ethane.Wang etc. will have unsatuated metal position for the first time
Cu-BTC for adsorbing separation ethylene-ethane [K. Schlichte, T. Kratzke, S. Kaskel,Microporous and Mesoporous Materials 2004, 73, 81-88.].Research finds that Cu-BTC has shown Preferential adsorption ethylene
Characteristic, reason be considered as in Cu-BTC copper ion can interact with the pi-electron in ethylene molecule.J. Geier
Deng discovery M2(dobdc) the unsatuated metal position of (M=Mg, Mn, Fe, Co, Ni, Zn) middle-high density makes it to ethylene second
The separation of alkane has excellent separating property [S. J. Geier, J. A. Mason, E. D. Bloch, W. L.
Queen, M. R. Hudson, C. M. Brown, J. R. Long, Chemical Science 2013, 4, 2054-
2061.].Under the conditions of 45 DEG C and 100 kPa, Fe2(dobdc) mixture of reciprocity molar ethylene ethane, the suction of ethylene/ethane
Attached selectivity may be up to about 14.
But because π complex bonds belong to weak chemical bond, the adsorbent of Preferential adsorption ethylene can still compare in desorption process
Compared with energy consumption.And due in the mixture of industrial ethylene-ethane ethylene belong to the higher component of content, use Preferential adsorption
The adsorbent floor space of ethylene can be larger, and the cost of adsorbent will also increase.In order to reduce energy consumption, Preferential adsorption is developed
The adsorbent of ethane has great importance.Choi etc. report a kind of activated carbon of Preferential adsorption ethane [B.-U. Choi,
D.-K. Choi, Y.-W. Lee, B.-K. Lee, S.-H. Kim, Journal of Chemical & Engineering Data 2003, 48, 603-607.], under 30 DEG C and 100 kPa, to the adsorption capacity of ethylene and ethane
Respectively 2.84 and 2.18 mmol/g, but the material exists not high to the adsorption capacity of ethane and ethylene and is adsorbed to ethane/ethylene
The problem of poor selectivity.Liang etc. has found Ni (bdc) (ted)0.5Show characteristic [the W. Liang, F. of Preferential adsorption ethane
Xu, X. Zhou, J. Xiao, Q. Xia, Y. Li, Z. Li, Chemical Engineering Science
2016, 148, 275-281.], under 25 DEG C and 100 kPa, the adsorption capacity to ethylene and ethane is respectively 3.4 and 5.0
Structure is easy to cave in air for mmol/g, adsorptive selectivity 1.85, but material exposure.
Invention content
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of double ligands of the iron-based of Preferential adsorption ethane
Metal-organic framework materials and the preparation method and application thereof.
Double ligand metal the organic framework material [(Fe of the iron-based of the present invention3O)(bdc)3(ted)1.5], it is by iron cluster Fe3
(CH3COO)6The porous material with delaminated structure to be formed is coordinated with terephthalic acid (TPA) and triethylene diamine.(Fe3O)(bdc)3
(ted)1.5There is high adsorption capacity to ethane and ethylene, mainly the specific surface area high with it and its pore size appropriate have
It closes.The material Preferential adsorption ethane is mainly since the pore size of the material is all bigger than ethane and ethylene, due to point of ethane
Sub- size（0.444 nm）Than the molecular dimension of ethylene（0.416 nm）Greatly, so material duct inner wall makees the Van der Waals of ethane
With compare ethylene it is stronger.In addition, polarizability bigger of the polarizability of ethane than ethylene, leads to absorption of the material skeleton to ethane
The bigger of force ratio ethylene.Importantly, since the chemical bond between high-valency metal iron and organic ligand is very strong, lead to this
The steam of material has good stability, and exposure can be stabilized in air.(Fe3O)(bdc)3(ted)1.5With Preferential adsorption second
Alkane, it is high to the adsorption capacity of ethane and ethylene, it is good to ethane/ethylene adsorptive selectivity, and steam has good stability the advantages that, it is right
In the separation of industrial ethylene-ethane, have a good application prospect.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of new iron-based double ligand metal organic framework materials of Preferential adsorption ethane, including following step
Suddenly：
（1）Synthesize iron cluster：By anhydrous sodium acetate and Fe (NO3)3·9H2O is dissolved in water respectively, obtains sodium acetate solution and nitric acid
Ferrous solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, is stirred, form suspension；Suspension is filtered again, and
It is washed successively with water and ethyl alcohol, is finally putting into baking oven and dries, obtain iron cluster [Fe3(CH3COO)6]；It is specifically shown in [D. Feng, K.
Wang, Z. Wei, Y. P. Chen, C. M. Simon, R. K. Arvapally, R. L. Martin, M.
Bosch, T. F. Liu, S. Fordham, D. Yuan, M. A. Omary, M. Haranczyk, B. Smit, H.
C. Zhou, Nature communications 2014, 5, 5723.]
（2）The double ligand metal organic framework materials of synthesis iron base：Terephthalic acid (TPA) and triethylene diamine are dissolved in N, N- diformazans
In base formamide (DMF), mixed solution is formed；Instill the N,N-dimethylformamide (DMF) of iron cluster dropwise into mixed solution
Solution, then glacial acetic acid is added dropwise, and stir uniform to mixed liquor；Mixed liquor is packed into vial interior sealing, then into line program control
Warm solvent-thermal process reaction；Product is impregnated and washed using n,N-Dimethylformamide (DMF) after reaction, is centrifuged
Filtering extraction, is placed in oven and dried, and obtains the double ligand metal organic framework materials of iron-based, is labeled as (Fe3O)(bdc)3
(ted)1.5。
Preferably, step（2）The mass ratio of the glacial acetic acid/triethylene diamine/terephthalic acid (TPA)/iron cluster is 1:(18~
24):(36~45):(152~165)。
Preferably, the vial volume is 30 mL, and bottle cap can still keep good seal performance at 130 DEG C；
Preferably, step（2）The temperature programmed control process of solvent-thermal process reaction is：
The temperature programming stage：Heating rate is set as 3 ~ 5 DEG C/min, mixed liquor is risen to 115 ~ 130 DEG C from room temperature；
The constant temperature stage：The temperature of mixed liquor keeps 36 ~ 60 h at 115 ~ 130 DEG C;
Program temperature-fall period：If rate of temperature fall is 0.2 ~ 0.8 DEG C/min, reaction solution is down to 30 ~ 40 DEG C from 115 ~ 130 DEG C.
Preferably, step（2）The DMF soaking times are 36 ~ 72 h.
Preferably, step（2）The rotating speed of the centrifugation is 5000 ~ 10000 r/min, and the time of centrifugation is 3 ~ 8 min.
Preferably, step（2）The temperature of the drying is 70 ~ 100 DEG C.
A kind of new iron-based double organic bones of ligand metal of Preferential adsorption ethane made from above-described preparation method
Frame material；The double ligand metal organic framework materials of the iron-based are applied in the separation of industrial ethane and ethylene.
Compared with prior art, the invention has the advantages that and technique effect：
1. the adsorbent Preferential adsorption ethane of the present invention, under normal temperature and pressure, the adsorption capacity of ethane is higher than ethylene.
2. the steam of adsorbent of the present invention has good stability, it is exposed to 60 days structures in humid air and remains unchanged.
3. the adsorbent of the present invention has high adsorption capacity and good adsorptive selectivity to ethane and ethylene, can be efficient
Detach ethane and ethylene.
Description of the drawings
Fig. 1 is the (Fe prepared by the embodiment of the present invention 1 ~ 43O)(bdc)3(ted)1.5-1、(Fe3O)(bdc)3
(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 XRD diagram.
Fig. 2 is the (Fe prepared by the embodiment of the present invention 1 ~ 43O)(bdc)3(ted)1.5-1、(Fe3O)(bdc)3
(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 thermal stability curve graph.
Fig. 3 is (Fe of the ethylene-ethane prepared by the embodiment of the present invention 13O)(bdc)3(ted)1.5Adsorption isotherm on -1
Line curve graph.
Fig. 4 is the (Fe prepared by the embodiment of the present invention 13O)(bdc)3(ted)1.5- 1 exposure different time in air
XRD diagram.
Fig. 5 is the (Fe prepared by the embodiment of the present invention 23O)(bdc)3(ted)1.5- 2 exposures different time in air
XRD diagram.
Fig. 6 is the (Fe prepared by the embodiment of the present invention 33O)(bdc)3(ted)1.5- 3 exposures different time in air
XRD diagram.
Fig. 7 is the (Fe prepared by the embodiment of the present invention 43O)(bdc)3(ted)1.5- 4 exposures different time in air
XRD diagram.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
（1）Synthesize iron cluster：By 25.4262 g anhydrous sodium acetates and 8.08 g Fe (NO3)3·9H2O is dissolved in 50 mL water respectively
In, obtain sodium acetate solution and iron nitrate solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, stirs 12 h, shape
At suspension；Suspension is filtered into obtain red brown solid again, and is washed successively with 50 mL deionized waters and 50 mL ethyl alcohol, finally
Product is put into 12 h of freeze-day with constant temperature under 70 DEG C of vacuum drying chambers, obtains iron cluster [Fe3(CH3COO)6]。
（2）The double ligand metal organic framework materials of synthesis iron base：By 60 mg terephthalic acid (TPA)s and 33 mg triethylene diamines
It is dissolved in 5 mL DMF, forms a kind of mixed solution；It instills 10 mL dropwise into mixed solution and dissolves 242 mg iron clusters
DMF solution, then 1.525 mg glacial acetic acid are added dropwise, and it is uniform to mixed liquor to stir 30 min；Mixed liquor is packed into 30 mL vials
Then interior sealing carries out temperature programmed control solvent-thermal process reaction；Solvent-thermal process reaction temperature programmed control process be：Temperature programming
Stage：Heating rate is set as 3 DEG C/min, mixed liquor is risen to 120 DEG C from room temperature；The constant temperature stage：The temperature of mixed liquor exists
120 DEG C of 48 h of holding;Program temperature-fall period：If rate of temperature fall is 0.2 DEG C/min, reaction solution is down to 35 DEG C from 120 DEG C.
80 ml DMF are used to impregnate 36 h of product after reaction, every 12 h replaces a solvent during immersion, then product after impregnating
Washing, then centrifugal filtration extraction, centrifugation rate are 8000 r/min, and centrifugation time is 5 min；Then product is put into 80 DEG C of bakings
It is dry in case, the double ligand metal organic framework materials of iron-based are obtained, (Fe is labeled as3O)(bdc)3(ted)1.5-1。
Embodiment 2
（1）Synthesize iron cluster：By 25.4262 g anhydrous sodium acetates and 8.08 g Fe (NO3)3·9H2O is dissolved in 50 mL water respectively
In, obtain sodium acetate solution and iron nitrate solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, stirs 12 h, shape
At suspension；Suspension is filtered into obtain red brown solid again, and is washed successively with 50 mL deionized waters and 50 mL ethyl alcohol, finally
Product is put into 12 h of freeze-day with constant temperature under 70 DEG C of vacuum drying chambers, obtains iron cluster [Fe3(CH3COO)6]。
（2）The double ligand metal organic framework materials of synthesis iron base：By tri- second of 53.375 mg terephthalic acid (TPA)s and 27.45 mg
Alkene diamines is dissolved in 5 mL DMF, forms a kind of mixed solution；Instill 10 mL dissolvings 228.75 dropwise into mixed solution
The DMF solution of mg iron clusters, then 1.525 mg glacial acetic acid are added dropwise, and it is uniform to mixed liquor to stir 30 min；Mixed liquor is packed into 30
Then mL vial interior sealings carry out temperature programmed control solvent-thermal process reaction；Solvent-thermal process reaction temperature programmed control process be：
The temperature programming stage：Heating rate is set as 3 DEG C/min, mixed liquor is risen to 115 DEG C from room temperature；The constant temperature stage：Mixed liquor
Temperature keeps 36 h at 115 DEG C;Program temperature-fall period：If rate of temperature fall is 0.2 DEG C/min, reaction solution is dropped from 115 DEG C
To 30 DEG C.80 ml DMF are used to impregnate 36 h of product after reaction, every 12 h replaces a solvent during immersion, then will leaching
Product washs after bubble, then centrifugal filtration extraction, and centrifugation rate is 5000 r/min, and centrifugation time is 3 min；Then product is put
Enter drying in 70 DEG C of baking ovens, obtains the double ligand metal organic framework materials of iron-based, be labeled as (Fe3O)(bdc)3(ted)1.5-2。
Embodiment 3
（1）Synthesize iron cluster：By 25.4262 g anhydrous sodium acetates and 8.08 g Fe (NO3)3·9H2O is dissolved in 50 mL water respectively
In, obtain sodium acetate solution and iron nitrate solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, stirs 12 h, shape
At suspension；Suspension is filtered into obtain red brown solid again, and is washed successively with 50 mL deionized waters and 50 mL ethyl alcohol, finally
Product is put into 12 h of freeze-day with constant temperature under 70 DEG C of vacuum drying chambers, obtains iron cluster [Fe3(CH3COO)6]。
（2）The double ligand metal organic framework materials of synthesis iron base：By tri- second of 68.625 mg terephthalic acid (TPA)s and 36.6 mg
Alkene diamines is dissolved in 5 mL DMF, forms a kind of mixed solution；Instill 10 mL dissolvings 251.625 dropwise into mixed solution
The DMF solution of mg iron clusters, then 1.525 mg glacial acetic acid are added dropwise, and it is uniform to mixed liquor to stir 30 min；Mixed liquor is packed into 30
Then mL vial interior sealings carry out temperature programmed control solvent-thermal process reaction；Solvent-thermal process reaction temperature programmed control process be：
The temperature programming stage：Heating rate is set as 5 DEG C/min, mixed liquor is risen to 130 DEG C from room temperature；The constant temperature stage：Mixed liquor
Temperature keeps 60 h at 130 DEG C;Program temperature-fall period：If rate of temperature fall is 0.8 DEG C/min, reaction solution is dropped from 130 DEG C
To 40 DEG C.80 ml DMF are used to impregnate 48 h of product after reaction, every 12 h replaces a solvent during immersion, then will leaching
Product washs after bubble, then centrifugal filtration extraction, and centrifugation rate is 10000 r/min, and centrifugation time is 8 min；Then by product
It is put into drying in 100 DEG C of baking ovens, the double ligand metal organic framework materials of iron-based is obtained, is labeled as (Fe3O)(bdc)3(ted)1.5-3。
Embodiment 4
（1）Synthesize iron cluster：By 25.4262 g anhydrous sodium acetates and 8.08 g Fe (NO3)3·9H2O is dissolved in 50 mL water respectively
In, obtain sodium acetate solution and iron nitrate solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, stirs 12 h, shape
At suspension；Suspension is filtered into obtain red brown solid again, and is washed successively with 50 mL deionized waters and 50 mL ethyl alcohol, finally
Product is put into 12 h of freeze-day with constant temperature under 70 DEG C of vacuum drying chambers, obtains iron cluster [Fe3(CH3COO)6]。
（2）The double ligand metal organic framework materials of synthesis iron base：By 61 mg terephthalic acid (TPA)s and 32.025 mg triethylenes
Diamines is dissolved in 5 mL DMF, forms a kind of mixed solution；Instill 10 mL dissolvings 240.1875 dropwise into mixed solution
The DMF solution of mg iron clusters, then 1.525 mg glacial acetic acid are added dropwise, and it is uniform to mixed liquor to stir 30 min；Mixed liquor is packed into 30
Then mL vial interior sealings carry out temperature programmed control solvent-thermal process reaction；Solvent-thermal process reaction temperature programmed control process be：
The temperature programming stage：Heating rate is set as 5 DEG C/min, mixed liquor is risen to 120 DEG C from room temperature；The constant temperature stage：Mixed liquor
Temperature keeps 60 h at 120 DEG C;Program temperature-fall period：If rate of temperature fall is 0.2 DEG C/min, reaction solution is dropped from 120 DEG C
To 30 DEG C.80 ml DMF are used to impregnate 36 h of product after reaction, every 12 h replaces a solvent during immersion, then will leaching
Product washs after bubble, then centrifugal filtration extraction, and centrifugation rate is 8000 r/min, and centrifugation time is 5 min；Then product is put
Enter drying in 80 DEG C of baking ovens, obtains the double ligand metal organic framework materials of iron-based, be labeled as (Fe3O)(bdc)3(ted)1.5-4。
(1) (Fe3O)(bdc)3(ted)1.5The pore structure property of the double ligand metal organic framework materials of iron-based
Using U.S.'s Micro companies ASAP-2460 specific surface pore-size distribution instrument to prepared by 1-4 of the embodiment of the present invention
(Fe3O)(bdc)3(ted)1.5-1、(Fe3O)(bdc)3(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3
(ted)1.5- 4 pore structure is characterized, and the results are shown in Table 1.
Table 1
As can be seen from Table 1, (Fe prepared by the present invention3O)(bdc)3(ted)1.5The double ligand metal organic framework materials of iron-based
BET specific surface area is about in 1436-1733 m2/ g, total pore volume are up to 0.68 cm3/ g, aperture are about distributed in 0.5nm or so,
This illustrates that four kinds of embodiments of the present invention are poromerics；And the aperture of the material is more moderate, it is more dynamic than ethylene and ethane
Aerodynamic diameter is bigger, and specific surface area and hole appearance are relatively high, therefore will have preferable absorption property to ethane and ethylene.
(2) (Fe3O)(bdc)3(ted)1.5Crystal structure properties
Using Philips XPERT types X-ray diffractometers to the (Fe prepared by 1-4 of the embodiment of the present invention3O)(bdc)3
(ted)1.5-1、(Fe3O)(bdc)3(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4
Crystal structure is characterized respectively, and wherein operating condition is：Cu targets KαLight source radiates 40 mA of intraductal electric current, 40 kv of voltage,
Continuous scanning mode, ranging from 5-50 ° of scanning angle, sweep speed are 1 °/min, and scanning step is 0.02 °.
(the Fe prepared by 1-4 of the embodiment of the present invention is shown in Fig. 13O)(bdc)3(ted)1.5-1、(Fe3O)(bdc)3
(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 XRD spectra, it will be seen from figure 1 that
Four kinds of (Fe3O)(bdc)3(ted)1.5Sample all has similar XRD spectra, and main feature peak position is identical, this four kinds of explanation
Under the conditions of synthesized substance crystal structure having the same.
(3) (Fe3O)(bdc)3(ted)1.5Thermal stability
Using the thermogravimetric analyzer of Netzsch STA 449F3 to the Fe prepared by 1-4 of the embodiment of the present invention3O)(bdc)3
(ted)1.5-1、(Fe3O)(bdc)3(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 into
Row thermal stability characterizes, and operating condition is：20 DEG C of initial temperature, 680 DEG C of final temperature, 5 DEG C/min of heating rate, nitrogen
40 mL/min of throughput.
Fe prepared by 1-4 of the embodiment of the present invention is shown in Fig. 23O)(bdc)3(ted)1.5-1、(Fe3O)(bdc)3
(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 thermogravimetric curve, can from Fig. 2
Go out, four kinds of (Fe3O)(bdc)3(ted)1.5Sample occurs weightless three times：Ranging from 150 DEG C of first stage weightless temperature with
Before, this stage is mainly DMF in the duct of material hole and the gas of adsorption and losing for steam；The weightless temperature of second stage
Ranging from 150 DEG C ~ 325 DEG C of degree, which is mainly losing for ligand triethylene diamine, illustrates its skeleton structure at this stage
Start to cave in；Ranging from 325 DEG C ~ 440 DEG C of phase III weightless temperature, the mainly decomposition of ligand terephthalic acid (TPA).
(4) (Fe3O)(bdc)3(ted)1.5Ethylene-ethane adsorption isotherm
The adsorption isotherm of ethane and ethylene is measured using U.S.'s Micro companies 3Flex vapor sorption instrument.Fig. 3 is ethylene under 298 K
(Fe of the ethane prepared by the embodiment of the present invention 13O)(bdc)3(ted)1.5Adsorption isotherm on -1.Locate in advance before sample test
Manage bar part is：Sample is vacuumized into 8 h of degassing at 80 DEG C.From figure 3, it can be seen that (the Fe at 298 K and 100 kPa3O)
(bdc)3(ted)1.5The adsorption capacity of -1 pair of ethane and ethylene is respectively 7.33 and 5.87 mmol/g.It is apparent that the suction of ethane
Attached amount illustrates the material Preferential adsorption ethane than the higher of ethylene.In addition, the adsorption capacity of the material is higher, the absorption of ethane
Capacity is about 2.6 times of traditional activated carbon.
(5) (Fe3O)(bdc)3(ted)1.5Steam stability
Using Philips XPERT types X-ray diffractometers to the (Fe prepared by the embodiment of the present invention 13O)(bdc)3
(ted)1.5- 1 carries out steam stability characterization, and wherein operating condition is：Cu targets KαLight source radiates 40 mA of intraductal electric current, voltage
40 kv, continuous scanning mode, ranging from 5-50 ° of scanning angle, sweep speed are 1 °/min, and scanning step is 0.02 °.
By (the Fe prepared by embodiment it can be seen from Fig. 4, Fig. 5, Fig. 6, Fig. 71 ~ 43O)(bdc)3(ted)1.5-1、
(Fe3O)(bdc)3(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 be exposed to it is relatively wet
The XRD diagram obtained after 7,20 or 60 days in the humid air that degree is 80% and the XRD for being not exposed to material in air are almost the same,
The characteristic diffraction peak of material still exists, and illustrates to be exposed in humid air after 60 days, the crystal framework structure of material does not have substantially
It changes, keeps original pore structure.Illustrate (the Fe prepared by embodiment 1 ~ 43O)(bdc)3(ted)1.5-1、(Fe3O)
(bdc)3(ted)1.5-2、(Fe3O)(bdc)3(ted)1.5- 3 and (Fe3O)(bdc)3(ted)1.5- 4 steam have good stability.
Claims (9)
1. a kind of preparation method of the double ligand metal organic framework materials of iron-based of Preferential adsorption ethane, which is characterized in that including
Following steps：
(1) iron cluster is synthesized：By anhydrous sodium acetate and Fe (NO3)3·9H2O is dissolved in water respectively, obtains sodium acetate solution and nitric acid
Ferrous solution；Then sodium acetate solution is instilled in iron nitrate solution dropwise, is stirred, form suspension；Suspension is filtered again, is washed
It washs, dries, obtain iron cluster；
(2) the double ligand metal organic framework materials of synthesis iron base：Terephthalic acid (TPA) and triethylene diamine are dissolved in DMF, shape
At mixed solution；It instills the DMF solution of iron cluster dropwise into the mixed solution, then glacial acetic acid is added dropwise, and stir to mixed liquor
Uniformly；Mixed liquor is packed into vial interior sealing, then carries out temperature programmed control solvent-thermal process reaction；It uses after reaction
DMF is impregnated and is washed to product, centrifugal filtration extraction, dry, is obtained the double ligand metal organic framework materials of iron-based, is labeled as
(Fe3O)(bdc)3(ted)1.5。
2. preparation method according to claim 1, which is characterized in that step（2）Glacial acetic acid/the triethylene diamine/right
The mass ratio of phthalic acid/iron cluster is 1:(18~24):(36~45):(152~165).
3. preparation method according to claim 1, which is characterized in that step（2）The program of the solvent-thermal process reaction
Temperature control process is：
The temperature programming stage：Heating rate is set as 3 ~ 5 DEG C/min, mixed liquor is risen to 115 ~ 130 DEG C from room temperature；
The constant temperature stage：The temperature of mixed liquor keeps 36 ~ 60 h at 115 ~ 130 DEG C;
Program temperature-fall period：Rate of temperature fall is set as 0.2 ~ 0.8 DEG C/min, mixed liquor is down to 30 ~ 40 DEG C from 115 ~ 130 DEG C.
4. preparation method according to claim 1, which is characterized in that step（2）The time of the immersion is 36 ~ 72 h.
5. preparation method according to claim 1, which is characterized in that step（2）The rotating speed of the centrifugation be 5000 ~
10000 r/min。
6. preparation method according to claim 1, which is characterized in that step（2）The time of the centrifugation is 3 ~ 8 min.
7. preparation method according to claim 1, which is characterized in that step（2）The temperature of the drying is 70 ~ 100 DEG C.
8. a kind of double ligand metals of the iron-based of Preferential adsorption ethane made from claim 1-7 any one of them preparation methods
Organic framework material.
9. a kind of double ligand metal organic framework materials of the iron-based of Preferential adsorption ethane described in claims 8 are applied to ethylene
In the separation of ethane.
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